US6150490A - Biologically degradable polyester, materials made from the polyester and production process - Google Patents
Biologically degradable polyester, materials made from the polyester and production process Download PDFInfo
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- US6150490A US6150490A US09/043,011 US4301198A US6150490A US 6150490 A US6150490 A US 6150490A US 4301198 A US4301198 A US 4301198A US 6150490 A US6150490 A US 6150490A
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- polyester
- aliphatic
- acid
- polycarboxylic acid
- diisocyanate
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- 229920000728 polyester Polymers 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title abstract description 37
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000002253 acid Substances 0.000 claims abstract description 34
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 229920001634 Copolyester Polymers 0.000 claims abstract description 20
- 244000005700 microbiome Species 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920000229 biodegradable polyester Polymers 0.000 claims abstract description 11
- 239000004622 biodegradable polyester Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 26
- -1 aliphatic polyol Chemical class 0.000 claims description 23
- 229920005862 polyol Polymers 0.000 claims description 21
- 239000000155 melt Substances 0.000 claims description 17
- 150000003077 polyols Chemical class 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011256 inorganic filler Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012766 organic filler Substances 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 235000010215 titanium dioxide Nutrition 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims 3
- 235000010980 cellulose Nutrition 0.000 claims 1
- 239000000945 filler Substances 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000012948 isocyanate Substances 0.000 abstract description 5
- 150000002513 isocyanates Chemical class 0.000 abstract description 4
- 150000005846 sugar alcohols Polymers 0.000 abstract 3
- 230000000306 recurrent effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 229920001817 Agar Polymers 0.000 description 9
- 239000008272 agar Substances 0.000 description 9
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- 239000002361 compost Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 229920003232 aliphatic polyester Polymers 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 239000007003 mineral medium Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
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- 238000006068 polycondensation reaction Methods 0.000 description 2
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- 239000000243 solution Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 206010011416 Croup infectious Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 230000000035 biogenic effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
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- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
Definitions
- the invention relates to biodegradable copolyesters of aliphatic and aromatic dicarboxylic acids with high molecular weights (in particular in the form of a material or substance to be processed further) and materials consisting of the polyester and a method of production.
- thermoformable polymeric materials have been developed in recent years which can be decomposed biologically by microorganisms.
- initial batches of mixtures of conventional olefinic polymers with starch (Krupp et al in Environ. Sci. Technol., 26 (1992) 193-1981) exhibited good application properties, they proved to be only partially degradable since only the starch content was metabolised by microorganisms.
- Biodegradable materials which are obtained directly or after suitable modification (Utz et al., Leten Kurs bioabbaubarer Kunststoffe immaschines Symposium--investigations on the use of biodegradable plastics in the packaging sector (1991), ), BMFT research report no.
- a solution to these problems can be achieved by using synthetic polymers.
- polymers exhibiting hetero atoms in their main chain have, in general, proved to be potentially biodegradable.
- aliphatic polyesters in particular, are metabolised by microorganisms within relatively short periods of time (Witt et al. in Makromol. Chem. Phys., 195 (1194) 793-802); however, such polyesters frequently exhibit only moderate thermal and mechanical properties.
- the aliphatic polyester polycaprolactone for example, has a melting point of only approximately 60° C., making it unsuitable for various applications.
- polyesters and polyamides can be improved by increasing the molecular weight by coupling them with diisocyanates, bisoxiranes or peroxides (DE A 1 495 714.3, DE A 2 011 678.3).
- diisocyanates bisoxiranes or peroxides
- EP A 0 572 256 Such a modified aliphatic polyester which is referred to as being biodegradable, is described in EP A 0 572 256.
- diisocyanates have been added in quantities of 0.1 to 5%.
- the thermal properties of the aliphatic polyester however, remain largely unaffected by such a modification.
- the use of aliphatic polyester urethanes containing up to 25% urethane segments, as biodegradable substances is also described (EP A 0 593 975).
- Aliphatic/aromatic copolyesters with terephthalic acid contents of 40 to 85 mole % have not been described as materials for further processing but for use as melt adhesives or coating agents in powder form (EP A 0 028 687), the biodegradability not being discussed in further detail.
- German patent application (1) 95 08 737.2 it was shown that it is possible to produce random copolyesters from aliphatic dicarboxylic acids and terephthalic acid and various aliphatic dicarboxylic acids and terephthalic acid as well as various aliphatic diols, which copolyesters exhibit satisfactory processing and application properties and, on the other hand, are biodegradable.
- An essential structural criterion of these materials consists in that the proportion of vicinal dicarboxylic acid units is kept small in order to guarantee the biodegradability of the copolyesters.
- These copolyesters produced by conventional melt condensation can be processed into moulded parts by extrusion.
- melt viscosities are required for numerous other processing methods, e.g. the manufacture of blown films and blow moulded parts (Yokota et al in Doi & Fukuda (editors), Biodegradable Plastics and Polymers, Elsevier, New York, 1994).
- High melt viscosities require a high molecular weight of the copolyesters. Basically, this is achieved by increasing the molecular weight of the copolyesters by raising the temperature, further reducing the pressure and substantially longer reaction times during polycondensation. For industrial purposes, this process is not practicable because of the long reaction times and the thermal stress on the materials, in particular for copolyesters.
- the task leading to the present invention consisted of developing a material for further processing which exhibits both good processing and application characteristics and can be simultaneously degraded by ubiquitous microorganisms.
- biodegradable polyesters in particular in the form of a material or substance to be processed further
- biodegradable polyesters which are degraded in a natural environment under the influence of microorganisms and which are high molecular random copolyesters produced by means of an aliphatic polyol, an aromatic polycarboxylic acid and, simultaneously, an aliphatic polycarboxylic acid as monomer components and exhibit constitutional repeating units or recurring units which consist
- the polyesters according to the invention can be produced by adding, after the condensation of the aliphatic/aromatic copolyesters, 0.1 to 5% by weight and in particular 0.5 to 2% by weight of bifunctional isocyanates, based on the polyester, e.g. to the melt.
- Suitable diisocyanates are aliphatic, cycloaliphatic or aromatic diisocyanates, in particular hexamethylene diisocyanate.
- the polyester according to the invention may have a content, based on the aromatic polycarboxylic acid as monomer component, of 3 to 65 and in particular 35 to 55 mole % (based on the total acid in the form of monomer components). This characteristic is advantageous for the biodegradability.
- the polyester according to the invention may have been produced by the polyester being precondensed with
- an aliphatic diol in particular C 2-6 -diol, preferably 1,2-ethane diol, 1,2-propane diol, 1,3-propane diol, 1,4-butane diol, 2,3-butane diol or 1,6 hexane diol
- aromatic dicarboxylic acid preferably terephthalic acid and
- an aliphatic dicarboxylic acid in particular C 2-10 dicarboxylic acid, preferably adipic acid or sebacic acid and
- the polyester according to the invention may be producible by condensing the polyester by means of aromatic dicarboxylic acids and/or aliphatic dicarboxylic acids in the form of their methyl esters.
- the polyester according the invention can be produced by
- stage (ii) condensing the preliminary product with diisocyanate to form the end product.
- stage (i) reference can be made to German patent application (1) 95 08 737.2.
- stage (i) it is possible to condense to form a preliminary product with molecular weights of 5,000 to 60,000 g/mole and preferably 20,000 to 50,000 g/mole. It is also possible to condense in stage (ii) to form an end product with molecular weights of 60,000 to 350,000 g/mole and in particular 100,000 to 250,000 g/mole.
- Polyesters according to the invention may be characterised by melting points of 40 to 155° C. and in particular 90 to 155° C.
- Polyesters according to the invention may be characterised by high melt viscosities.
- an essential advantage of the polyesters according to the invention consists in that the thermal properties, the processing and mechanical properties and the rate of biodegradation can be adjusted within wide limits to suit the application concerned. This flexibility is guaranteed by possible variation of the monomer components and their proportions and of the parameters mentioned above.
- the polyesters according to the invention differ from those of German patent application (1) 95 08 737.2 in that they are precondensed polyesters.
- biodegradability of the polyesters according to the invention reference can be made to the above-mentioned German patent application. Surprisingly enough, the person skilled in the art has found that, in spite of the dramatic increase in the molecular weight of the polyesters according to the invention, it is possible to guarantee biodegradability by microorganisms by coupling by means of diisocyanates.
- polyester according to the invention in powder form is placed on an agar plate with a complex medium and inoculated with a microorganism consortium capable of biodegrading polyesters according to German patent application (1) 95 08 737.2 (pre-polyesters), clearly visible haloes are formed around the microorganism colonies also in the case of the polyesters according to the invention, e.g. at an incubation temperature of 55° C., within 7 days; regarding the degradation test, compare Augusta et al. in Appl. Microbiol. Biotechol., 39 (1993) 673-678.
- the present invention relates to a material consisting of a biodegradable polyester according to the invention in the form of
- moulded parts preferably injection moulded, extruded or foamed moulded parts, in particular blown films, extruded films, coextruded films, blow-moulded bodies, thermoformed bodies, foamed bodies or monofilamentous materials.
- Polyesters according to the invention can be processed, for example by thermoplastic processes such as compression moulding, extrusion, coextrusion, injection moulding, melt spinning, thermoforming, foaming or blow moulding into flat material, e.g. films, or into moulded parts or, by suitable methods, into foamed moulded parts, laminates, filamentous materials, fibres or composite materials.
- thermoplastic processes such as compression moulding, extrusion, coextrusion, injection moulding, melt spinning, thermoforming, foaming or blow moulding into flat material, e.g. films, or into moulded parts or, by suitable methods, into foamed moulded parts, laminates, filamentous materials, fibres or composite materials.
- polyesters according to the invention are chain-extended polymers which have substantially higher melt viscosities compared with the non-chain-extended copolyesters of the art, the polyesters according to the invention are suitable in particular for processing methods for which high melt viscosities are desirable, e.g. for blow moulding processes.
- Materials according to the invention may have a high mechanical strength. This mechanical strength can be increased by stretching at temperatures below the melting point.
- the invention finally relates to a process for the production of biodegradable polyesters which are degraded in a natural environment under the influence of microorganisms and which are high molecular random copolyesters produced by means of an aliphatic polyol, an aromatic polycarboxylic acid and, simultaneously, an aliphatic polycarboxylic acid as monomer components and exhibit constitutional repeating units or recurring units which consist
- polyol, aromatic carboxylic acid and aliphatic polycarboxylic acid are condensed in the melt to form a preliminary product and subsequently
- the preliminary product is condensed with a diisocyanate as additional monomer component to form the end product, the diisocyanate being used in a smaller quantity compared with that of each of the other monomer components.
- agar plates are prepared according to common sterile methods.
- Polymer The polymer concerned is dissolved to form a 1% solution in chloroform and sprayed with a fine nozzle in the form of fine particles onto the agar plate. To remove the chloroform, the plate is left to stand without a cover for some time under the clean bench.
- Organism Isolat (CH2/5) from an enriched culture with non-chain-extended degradable copolymers from compost at 60° C.
- the organism is transferred from an agar plate with non-chain-extended copolyester with an inoculation loop in dot form onto the agar plate holding the material to be tested and incubated at 55° C.
- the formation of haloes around the organism cultures, in which polymer material is no longer recognisable, is characterised by an average halo diameter.
- films of a thickness of 120 ⁇ m (diameter 2.5 cm) are produced from the materials according to the invention.
- the films are subjected to a biological charge as follows:
- the films are placed onto an agar plate with the synthetic mineral medium described above or a complex medium of a compost eluate.
- the inoculation takes place before placing the films by spreading the screened microorganism consortia onto the agar plate.
- the incubation temperature is 55° C.
- the weight loss of the films in percent is determined.
- the films are introduced into a reactor filled with fully ripened compost material (60% humidity) and externally thermostated at 60° C. (to allow a better relocation of the fragments, the films are enclosed in polyethylene nets).
- the reactor is aerated during the period of the test with pre-thermostated and steam-saturated air. The weight loss of the films is determined in percent.
- 358.3 g 1,4-butane diol, 308.9 g dimethyl terephthalate (DMT), 348.7 g adipic acid, 0.25 g tetraisopropyl orthotitanate and 0.25 g triphenyl phosphate are polycondensed by condensation in the melt.
- a 2 liter plane joint reactor with a vacuum agitator system, a nitrogen feed and a condenser is used as polycondensation vessel. The reactor is flushed out with nitrogen, the mixture is melted at 150° C. and condensed with stirring at 190° C. in the steam of nitrogen.
- the pressure is gradually reduced to approximately 0.1 hPa and the base powder is condensed to a molecular weight of 50,000 g/mole while being monitored by GPC.
- the vacuum is released and 0.5 g phosphorous acid is stirred into the melt.
- 15 g hexamethylene diisocyanate are added directly to the melt at 200° C. with stirring. Within a few minutes, a substantial increase in the viscosity of the melt takes place.
- the copolyester is subsequently discharged, cooled and granulated.
- a white flexible material with a weight average molecular weight of 168500 g/mole and a melting point of 109° C. is obtained. Films of this material produced by extrusion typically exhibit tensile strength values of 12 N/mm 2 and an elongation at break of 900%.
- 35.83 g 1.4-butane diol, 30.89 g dimethyl terephthalate (DMT), 34.87 g adipic acid and 0.025 g tetraisopropyl orthotitanate and 0.0.25 g triphenyl phosphate are condensed as in example 1 to a molecular weight of 48,000 g/mole.
- a 250 ml three-necked flask is used as the polymerisation reactor. After adding 0.05 g phosphorous acid, the copolyester is discharged, cooled and granulated.
- a white, flexible material with a weight average molecular weight of 232300 g/mole and a melting point of 107° C. is obtained.
- Films of this material produced by compression moulding of the melt typically exhibit tensile strength values of 16 N/mm 2 and an elongation at break of 600%.
- Granules from example 1 with an MFI (190/21.5) of 3.75 g/10 minutes are processed at a take-off speed of 2-3 m/min and with a blow-up ratio of 1:2 on the facility described above to form blown films.
- the films thus obtained exhibit properties comparable with LDPE as regards transparency and strength but a much higher extensibility.
- the invention relates to biodegradable polyesters which are degraded in a natural environment under the influence of microorganisms and which are high molecular random copolyesters produced by means of an aliphatic polyol, an aromatic polycarboxylic acid and, simultaneously, an aliphatic polycarboxylic acid as monomer components and exhibit constitutional repeating units or recurring units which consist
- polyol, aromatic polycarboxylic acid and aliphatic polycarboxylic acid are condensed in the melt to a preliminary product and subsequently
- the preliminary product is condensed with the diisocyanate as additional monomer component to form the end product, the diisocyanate being used in a smaller quantity compared with that of each of the other monomer components.
- the invention also relates to materials consisting of a biodegradable polyester according to the invention and a method of production for polyesters according to the invention.
Abstract
Description
______________________________________ Pump: Gynkotek, model 300C Detector: SDK Shodex RI SE-51 Column: PL gel, 10.sup.4 Å, 7.5 × 300 mm Calibration: PS - Standards PL-Laboratories; molecular weight 23000-990000 g/mole Solvent: Chloroform Flow rate 1 ml/min Polymer concentration: 1 mg/ml Injection volume: 50 μl ______________________________________
______________________________________ Equipment: Mettler DSC 12 Amount weighed in: 5-10 mg Temperature range: 20-200° C. Rate of heating: 10° C./min ______________________________________
______________________________________ Medium: ______________________________________ NH.sub.4 NO.sub.3 1.0 g MgSO.sub.4 * 7H.sub.2 O 0.5 g NaCl 0.5 g FeSO.sub.4 * 7H.sub.2 O 0.01 g K.sub.2 HPO.sub.4 1.0 g Agar 20.0 g ______________________________________
______________________________________ Equipment: Zwick flow test device 4105 Measuring load: 2.16-21.6 kg Measuring temperature: 150-220° C. ______________________________________
______________________________________ Equipment: Zwick universal test machine 1425 Size of the film strips: 50 × 15 mm Rate of take-off: 500 mm/min ______________________________________
______________________________________ Polymer Polymer according according to to Non-chain-extended Test method example 1 example 2 BTA ______________________________________ Compost test (a) (weight loss in %) after 4 weeks 38 ± 13 31 ± 5 -- after 8 weeks 78 ± 7 71 ± 11 Clear zone test 15 14 -- (zone diameter in mm after 7 days) Film/plate test 28 21 17 mineral medium organisms 2/5 (weight loss in % after 9 days) Film/plate test 39 50 56 compost eluate medium organisms 2/5 (weight loss in % after 9 days) Film/plate test 4 5 9 mineral medium organisms K1 (weight loss in % after 20 days) Film/plate test 32 26 17 mineral medium organisms K2 (weight loss in % after 20 days) Film/plate test No further film fragments to be isolated mineral medium organisms 2/5 (weight loss in % after 20 days) ______________________________________ a: mean of 3 measurements
______________________________________ Equipment: Dr. Collin laboratory blown film facility with small extruder Y30 mm × 25 D 3-zone screw with shearing and mixing section Compression ratio: 1:3 Annular die diameter: 80 mm Die gap width: 0.8 mm Distance between die and nip rolls 1.5 m Processing parameters: Screw: 200-255° C. Screen changer: 210° C. Adapter: 210° C. Die: 210° C. Melt temperature: 230° C. Melt pressure: 360 bar Screw speed: 25 min.sup.-1 ______________________________________
Claims (29)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19532771 | 1995-09-05 | ||
DE19532771A DE19532771A1 (en) | 1995-09-05 | 1995-09-05 | Biodegradable polyester, polyester materials and manufacturing process |
PCT/EP1996/003879 WO1997009364A1 (en) | 1995-09-05 | 1996-09-04 | Biologically degradable polyester, materials made from the polyester and production process |
Publications (1)
Publication Number | Publication Date |
---|---|
US6150490A true US6150490A (en) | 2000-11-21 |
Family
ID=7771329
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/043,011 Expired - Fee Related US6150490A (en) | 1995-09-05 | 1996-09-04 | Biologically degradable polyester, materials made from the polyester and production process |
Country Status (6)
Country | Link |
---|---|
US (1) | US6150490A (en) |
EP (1) | EP0848725A1 (en) |
JP (1) | JP2000501121A (en) |
AU (1) | AU7083896A (en) |
DE (1) | DE19532771A1 (en) |
WO (1) | WO1997009364A1 (en) |
Cited By (8)
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US6573340B1 (en) | 2000-08-23 | 2003-06-03 | Biotec Biologische Naturverpackungen Gmbh & Co. Kg | Biodegradable polymer films and sheets suitable for use as laminate coatings as well as wraps and other packaging materials |
US20030166779A1 (en) * | 2002-03-01 | 2003-09-04 | Kishan Khemani | Biodegradable polymer blends for use in making films, sheets and other articles of manufacture |
US20040248486A1 (en) * | 2003-06-03 | 2004-12-09 | Hodson Simon K. | Fibrous sheets coated or impregnated with biodegradable polymers or polymers blends |
KR100701622B1 (en) | 2005-02-24 | 2007-03-30 | 이규득 | Biodegradable aliphatic/aromatic copolyester polymer and preparation thereof |
US20070179253A1 (en) * | 2004-03-04 | 2007-08-02 | Unitika Ltd. | Biodegradable polyester resin composition, preparation method therefor, and foamed article and molded article produced therefrom |
US7297394B2 (en) | 2002-03-01 | 2007-11-20 | Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg | Biodegradable films and sheets suitable for use as coatings, wraps and packaging materials |
US20080188593A1 (en) * | 2005-03-18 | 2008-08-07 | Novamont S.P.A. | Biodegradable Aliphatic-Aromatic Polyester |
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DE19817883C1 (en) * | 1998-04-08 | 1999-11-25 | Monofil Technik Gmbh | Plastic cutting wire, used in e.g. rotating brush cutters |
DE102005053068B4 (en) * | 2005-11-04 | 2017-05-11 | Basf Se | Sebazic acid-containing polyester and polyester blend, process for their preparation and a Verzweigerbatch and the use of the polyester blend |
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- 1996-09-04 AU AU70838/96A patent/AU7083896A/en not_active Withdrawn
- 1996-09-04 US US09/043,011 patent/US6150490A/en not_active Expired - Fee Related
- 1996-09-04 JP JP51086397A patent/JP2000501121A/en active Pending
- 1996-09-04 EP EP96931768A patent/EP0848725A1/en not_active Withdrawn
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US20030166779A1 (en) * | 2002-03-01 | 2003-09-04 | Kishan Khemani | Biodegradable polymer blends for use in making films, sheets and other articles of manufacture |
US20050182196A1 (en) * | 2002-03-01 | 2005-08-18 | Biotec Biologische Naturverpackungen Gmb | Biodegradable polymer blends for use in making films, sheets and other articles of manufacture |
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Also Published As
Publication number | Publication date |
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WO1997009364A1 (en) | 1997-03-13 |
JP2000501121A (en) | 2000-02-02 |
DE19532771A1 (en) | 1997-03-06 |
AU7083896A (en) | 1997-03-27 |
EP0848725A1 (en) | 1998-06-24 |
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